Tan Xuerong, Zhao Bin, Lu Jianwei, Liu Shaoying, Gou Weini, Yang Rong, Zuo Peng
Guangyuan Center for Disease Control and Prevention, Guangyuan 628000, China.
Hangzhou Center for Disease Control and Prevention, Hangzhou 310006, China.
Se Pu. 2022 Jan;40(1):57-65. doi: 10.3724/SP.J.1123.2021.03010.
Chromatography combined with mass spectrometry is the most commonly used detection technology, and it offers the advantages of high sensitivity and high selectivity. However, the contents of bisphenols (BPs) in water samples are at the ng/L level. Even if the BPs contents are determined by mass spectrometry, the samples must be pretreated and enriched. A quick, easy, inexpensive, effective, rugged, and safe technique (QuEChERS) can offer advantages such as cost effectiveness and time efficiency. The application of QuEChERS is currently extended to the analysis of contaminants in food and water samples. In this work, QuEChERS coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was proposed for the determination of eight BPs in surface water. Method optimization was carried out in terms of process efficiency (PE), which included the matrix effect (ME) and extraction recovery (RE). First, the water samples were extracted with 10 mL ethyl acetate and cleaned with 50 mg primary secondary amine (PSA) and 50 mg graphitized carbon black (GCB). Then, the organic layer was collected and evaporated to dryness under nitrogen flow (40 ℃). Finally, the extracts were redissolved in 0.5 mL of a methanol-water (1∶1, v/v) mixture and subjected to UPLC-MS/MS analysis. Chromatographic separation was accomplished on a Waters ACQUITY UPLC BEH C column (100 mm×2.1 mm, 1.7 μm) with gradient elution. Methanol and 0.1 mmol/L ammonium bicarbonate aqueous solution were used as the mobile phases. The eight BPs were analyzed by MS/MS with negative electrospray ionization (ESI) and in the multiple reaction monitoring (MRM) mode. The matrix matching external standard method was used for quantitative determination. The eight compounds could be analyzed within 8 min. Under the optimized conditions, the calibration curves showed good linearities for the eight BPs, and the coefficients of determination () were greater than 0.9990. The limits of detection (LODs, =3) and limits of quantification (LOQs, =10) were in the ranges of 0.1-2.3 ng/L and 0.3-6.1 ng/L, respectively. The average recoveries of the eight BPs in river water samples were 78.8%-116.6%, and the corresponding relative standard deviations (RSDs) were 1.8%-9.0% (=6). This method was applied to the analysis of BPs pollution in Guangyuan section of Jialing river and its tributaries, and widespread pollution was confirmed. The detection rate of BPA was 100% with a content of 6.15-90.03 ng/L, and the detection rate of BPS was 91%, with the contents being in the range not detected (nd) to 4.63 ng/L. The method established in this study allowed for the rapid enrichment and purification of the eight BPs in water. With its advantages of simplicity, rapidness, high sensitivity, and low cost, the method can be used for the rapid determination of trace BPs in surface water such as lake water and river water.
色谱联用质谱是最常用的检测技术,具有高灵敏度和高选择性的优点。然而,水样中双酚类物质(BPs)的含量处于纳克/升水平。即使采用质谱法测定BPs含量,样品也必须进行预处理和富集。快速、简便、廉价、高效、耐用且安全的技术(QuEChERS)具有成本效益和时间效率等优势。目前,QuEChERS已扩展应用于食品和水样中污染物的分析。在本研究中,采用QuEChERS与超高效液相色谱 - 串联质谱联用(UPLC - MS/MS)法测定地表水中的8种双酚类物质。从过程效率(PE)方面进行了方法优化,过程效率包括基质效应(ME)和萃取回收率(RE)。首先,取水样10 mL用乙酸乙酯萃取,并用50 mg伯仲胺(PSA)和50 mg石墨化炭黑(GCB)净化。然后,收集有机层并在氮气流(40℃)下蒸发至干。最后,将提取物重新溶解于0.5 mL甲醇 - 水(1∶1,v/v)混合溶液中,进行UPLC - MS/MS分析。采用Waters ACQUITY UPLC BEH C18柱(100 mm×2.1 mm,1.7 μm)进行梯度洗脱实现色谱分离。甲醇和0.1 mmol/L碳酸氢铵水溶液作为流动相。采用负电喷雾电离(ESI)和多反应监测(MRM)模式通过MS/MS分析8种双酚类物质。采用基质匹配外标法进行定量测定。8种化合物可在8分钟内完成分析。在优化条件下,8种双酚类物质的校准曲线线性良好,决定系数(R²)大于0.9990。检测限(LODs,n = 3)和定量限(LOQs,n = 10)分别在0.1 - 2.3 ng/L和0.3 - 6.1 ng/L范围内。河流水样中8种双酚类物质的平均回收率为78.8% - 116.6%,相应的相对标准偏差(RSDs)为1.8% - 9.0%(n = 6)。该方法应用于嘉陵江广元段及其支流双酚类物质污染状况分析,证实存在广泛污染。双酚A(BPA)的检出率为100%,含量为6.15 - 90.03 ng/L,双酚S(BPS)的检出率为91%,含量在未检出(nd)至4.63 ng/L范围内。本研究建立的方法可对水中8种双酚类物质进行快速富集和净化。该方法具有简便、快速、高灵敏度和低成本的优点,可用于湖水、河水等地表水中痕量双酚类物质的快速测定。